JP4811436B2 - Thermoplastic elastomer composition and pneumatic tire using the same - Google Patents
Thermoplastic elastomer composition and pneumatic tire using the same Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0008—Compositions of the inner liner
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/008—Additives improving gas barrier properties
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
- C08K5/435—Sulfonamides
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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Description
本発明は、熱可塑性エラストマー組成物およびそれを用いた空気入りタイヤに関し、さらに詳しくは、脂肪族ポリアミド樹脂にエチレン系改質ポリマーを分散充填した熱可塑性エラストマー組成物およびそれを用いた空気入りタイヤに関する。 The present invention relates to a thermoplastic elastomer composition and a pneumatic tire using the same, and more particularly, a thermoplastic elastomer composition in which an ethylene-based modified polymer is dispersed and filled in an aliphatic polyamide resin and a pneumatic tire using the same. About.
従来、タイヤの内圧を保持するためにタイヤ内面に空気バリヤ層として配設されるインナーライナーには、ブチルゴムやハロゲン化ブチルゴム等を主原料とするゴム組成物が使用されている。しかしながら、これらブチル系ゴムを主原料とするゴム組成物は、空気バリヤ性が低いため、かかるゴム組成物をインナーライナーに使用した場合、インナーライナーの厚みを1〜4mm前後とする必要があり、タイヤに占めるインナーライナーの質量が約5%となり、タイヤの質量を低減して自動車の燃費を向上させる上で障害となっている。 Conventionally, a rubber composition mainly composed of butyl rubber, halogenated butyl rubber or the like is used for an inner liner disposed as an air barrier layer on the inner surface of the tire in order to maintain the internal pressure of the tire. However, since the rubber composition mainly composed of these butyl rubbers has low air barrier properties, when such a rubber composition is used for the inner liner, the thickness of the inner liner needs to be around 1 to 4 mm. The mass of the inner liner in the tire is about 5%, which is an obstacle to reducing the mass of the tire and improving the fuel efficiency of the automobile.
特定の熱可塑性樹脂マトリクス中に特定のゴムエラストマー成分を不連続相として分散させてなる、耐空気透過性と柔軟性とのバランスに優れた熱可塑性エラストマー組成物は知られている(特許文献1)。 A thermoplastic elastomer composition having a good balance between air permeation resistance and flexibility obtained by dispersing a specific rubber elastomer component as a discontinuous phase in a specific thermoplastic resin matrix is known (Patent Document 1). ).
また、当該熱可塑性エラストマー組成物における熱可塑性樹脂成分の溶融粘度(ηm)とゴムエラストマー成分の溶融粘度(ηd)および該エラストマー成分と熱可塑性樹脂成分の溶解性パラメーターの差(ΔSP)を特定の関係式を満たすようにすることで高エラストマー成分比率を達成し、それによって一層柔軟性に富み、耐気体透過性に優れた熱可塑性エラストマー組成物が得られること、そしてそれを気体透過防止層に使用した空気入りタイヤも知られている(特許文献2)。 Further, the difference (ΔSP) in the melt viscosity (η m ) of the thermoplastic resin component and the melt viscosity (η d ) of the rubber elastomer component and the solubility parameter of the elastomer component and the thermoplastic resin component in the thermoplastic elastomer composition By satisfying a specific relational expression, a high elastomer component ratio can be achieved, thereby obtaining a thermoplastic elastomer composition that is more flexible and excellent in gas permeation resistance, and prevents gas permeation. A pneumatic tire used for the layer is also known (Patent Document 2).
さらに、熱可塑性樹脂を連続相としゴム組成物を分散相とする熱可塑性エラストマー中に、偏平状に分散してなる相構造を有するバリヤ樹脂組成物を存在させることで、耐ガス透過性が大巾に向上して、しかも柔軟性、耐油性、耐寒性および耐熱性を有するような熱可塑性エラストマー組成物も知られている(特許文献3)。 Furthermore, the presence of a barrier resin composition having a phase structure in which a thermoplastic resin is a continuous phase and a rubber composition is a dispersed phase and a phase structure is formed in a flat shape, thereby increasing gas permeability resistance. A thermoplastic elastomer composition which is improved in width and has flexibility, oil resistance, cold resistance and heat resistance is also known (Patent Document 3).
さらに、層状珪酸塩で変性した脂肪族ポリアミド樹脂に酸無水物変性エチレン系改質ポリマーをブレンドした熱可塑性エラストマー組成物も知られている(特許文献4)。 Furthermore, a thermoplastic elastomer composition in which an anhydride-modified ethylene-based modified polymer is blended with an aliphatic polyamide resin modified with a layered silicate is also known (Patent Document 4).
しかし、層状珪酸塩で変性した脂肪族ポリアミド樹脂と酸無水物変性エチレン系改質ポリマーをブレンドした場合、ポリアミド樹脂と酸無水物基が反応するため、エチレン系改質ポリマーを高充填すると、溶融時の流動性が極端に低下し、フィルム製膜性が大幅に悪化する問題があった。
本発明は、脂肪族ポリアミド樹脂の低温耐久性(繰り返し疲労性)を改善するために、脂肪族ポリアミド樹脂マトリックス中に低温耐久性に優れるエチレン系改質ポリマーを分散充填した熱可塑性エラストマー組成物において、改質ポリマーを高充填しても流動性を維持し、フィルム製膜が可能であり、かつ低温耐久性に優れる熱可塑性エラストマー組成物を提供することを課題とする。
However, when an aliphatic polyamide resin modified with a layered silicate and an anhydride-modified ethylene-based modified polymer are blended, the polyamide resin reacts with the acid anhydride group. There was a problem that the fluidity at the time was extremely lowered and the film-forming property was greatly deteriorated.
The present invention relates to a thermoplastic elastomer composition in which an aliphatic polyamide resin matrix is dispersed and filled with an ethylene-based modified polymer excellent in low-temperature durability in order to improve low-temperature durability (repeated fatigue) of an aliphatic polyamide resin. It is an object of the present invention to provide a thermoplastic elastomer composition that maintains fluidity even when highly loaded with a modified polymer, can be formed into a film, and has excellent low-temperature durability.
本発明は、熱可塑性樹脂組成物(A)および酸無水物基でグラフト変性された変性エチレン系改質ポリマー(B)からなる熱可塑性エラストマー組成物であって、熱可塑性樹脂組成物(A)は層間重合法により作製した層状珪酸塩変性脂肪族ポリアミド樹脂(A1)60〜90質量%および溶解度パラメーター(SP値)が10〜12(cal/cm2)1/2である疎水性可塑剤(A2)10〜40質量%からなり、熱可塑性エラストマー組成物100質量部に対して変性エチレン系改質ポリマー(B)が70〜120質量部であり、変性エチレン系改質ポリマー(B)が分散粒子相を形成していることを特徴とする熱可塑性エラストマー組成物である。 The present invention is a thermoplastic elastomer composition comprising a thermoplastic resin composition (A) and a modified ethylene-based modified polymer (B) graft-modified with an acid anhydride group, the thermoplastic resin composition (A) Is a hydrophobic plasticizer having a layered silicate-modified aliphatic polyamide resin (A1) prepared by an interlayer polymerization method of 60 to 90% by mass and a solubility parameter (SP value) of 10 to 12 (cal / cm 2 ) 1/2 A2) 10 to 40% by mass of the modified ethylene-based modified polymer (B) is 70 to 120 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer composition, and the modified ethylene-based modified polymer (B) is dispersed. A thermoplastic elastomer composition characterized by forming a particle phase.
本発明において、前記疎水性可塑剤(A2)は、好ましくは、スルホンアミド系可塑剤である。
また、前記層状珪酸塩は、好ましくは、ナトリウム型モンモリロナイトである。
また、前記変性脂肪族ポリアミド樹脂(A1)は、好ましくは、0.5〜5質量%の層状珪酸塩で変性されている。
また、前記変性脂肪族ポリアミド樹脂(A1)を構成する脂肪族ポリアミド樹脂は、好ましくは、ナイロン6、ならびにε−カプロラクタム由来成分を90モル%以上含むナイロン610、ナイロン612、およびナイロン6.66からなる群から選択された少なくとも1種である。
また、前記変性エチレン系改質ポリマー(B)は、好ましくは、少なくとも分子中に2個以上のアミノ基を有する多官能アミンで架橋されている。
また、前記変性エチレン系改質ポリマー(B)は、好ましくは、エチレン−α−オレフィン共重合体および/またはエチレン−不飽和カルボン酸(誘導体)共重合体である。
In the present invention, the hydrophobic plasticizer (A2) is preferably a sulfonamide plasticizer.
The layered silicate is preferably sodium montmorillonite.
The modified aliphatic polyamide resin (A1) is preferably modified with 0.5 to 5% by mass of a layered silicate.
The aliphatic polyamide resin constituting the modified aliphatic polyamide resin (A1) is preferably nylon 6, and nylon 610, nylon 612, and nylon 6.66 containing 90 mol% or more of an ε-caprolactam-derived component. At least one selected from the group consisting of:
The modified ethylene-based modified polymer (B) is preferably crosslinked with a polyfunctional amine having at least two amino groups in the molecule.
The modified ethylene-based modified polymer (B) is preferably an ethylene-α-olefin copolymer and / or an ethylene-unsaturated carboxylic acid (derivative) copolymer.
本発明は、また、層間重合法により作製した層状珪酸塩変性脂肪族ポリアミド樹脂(A1)60〜90質量%および溶解度パラメーター(SP値)が10〜12(cal/cm2)1/2である疎水性可塑剤(A2)40〜10質量%からなる熱可塑性樹脂組成物(A)100質量部と、酸無水物基でグラフト変性された変性エチレン系改質ポリマー(B)70〜120質量部とを、前記熱可塑性樹脂組成物(A)および前記変性エチレン系改質ポリマー(B)の融解温度以上で溶融混合した後、多官能アミンで前記変性エチレン系改質ポリマー(B)を動的に架橋することを特徴とする熱可塑性エラストマー組成物の製造方法である。 In the present invention, the layered silicate-modified aliphatic polyamide resin (A1) prepared by an interlayer polymerization method is 60 to 90% by mass, and the solubility parameter (SP value) is 10 to 12 (cal / cm 2 ) 1/2 . 100 parts by mass of the thermoplastic resin composition (A) comprising 40 to 10% by mass of the hydrophobic plasticizer (A2) and 70 to 120 parts by mass of the modified ethylene-based modified polymer (B) graft-modified with an acid anhydride group Is melt-mixed at a temperature equal to or higher than the melting temperature of the thermoplastic resin composition (A) and the modified ethylene-based modified polymer (B), and then the modified ethylene-based modified polymer (B) is dynamically mixed with a polyfunctional amine. It is a method for producing a thermoplastic elastomer composition characterized by cross-linking.
本発明は、また、前記熱可塑性エラストマー組成物からなるフィルムをインナーライナーとして用いた空気入りタイヤである。 The present invention also provides a pneumatic tire using a film made of the thermoplastic elastomer composition as an inner liner.
本発明によれば、ポリアミド樹脂(A1)として、層状珪酸塩変性ポリアミド樹脂を用い、それに疎水性可塑剤(A2)を含有させ、さらに変性エチレン系改質ポリマー(B)を配合することにより、成分(A1)および(A2)のマトリックス相に成分(B)を分散相として分散させ、分散相の充填量を増加させつつ溶融粘度の上昇を抑制することが可能となり、その結果としてガスバリヤ性、耐疲労性、および溶融加工性に優れた熱可塑性エラストマー組成物を得ることができる。
また、本発明の熱可塑性エラストマー組成物からなるフィルムは、インナーライナーとして空気入りタイヤに用いることができる。
According to the present invention, by using a layered silicate-modified polyamide resin as the polyamide resin (A1), containing a hydrophobic plasticizer (A2), and further blending a modified ethylene-based modified polymer (B), It is possible to disperse the component (B) as a dispersed phase in the matrix phase of the components (A1) and (A2), and to suppress an increase in melt viscosity while increasing the filling amount of the dispersed phase. As a result, gas barrier properties, A thermoplastic elastomer composition having excellent fatigue resistance and melt processability can be obtained.
Moreover, the film which consists of a thermoplastic elastomer composition of this invention can be used for a pneumatic tire as an inner liner.
本発明の熱可塑性エラストマー組成物は、熱可塑性樹脂組成物(A)および酸無水物基でグラフト変性された変性エチレン系改質ポリマー(B)からなり、熱可塑性樹脂組成物(A)は層間重合法により作製した層状珪酸塩変性脂肪族ポリアミド樹脂(A1)60〜90質量%および溶解度パラメーター(SP値)が10〜12(cal/cm2)1/2である疎水性可塑剤(A2)40〜10質量%からなる。 The thermoplastic elastomer composition of the present invention comprises a thermoplastic resin composition (A) and a modified ethylene-based modified polymer (B) graft-modified with an acid anhydride group, and the thermoplastic resin composition (A) is an interlayer. Hydrophobic plasticizer (A2) having a layered silicate-modified aliphatic polyamide resin (A1) produced by a polymerization method of 60 to 90% by mass and a solubility parameter (SP value) of 10 to 12 (cal / cm 2 ) 1/2 It consists of 40-10 mass%.
本発明において使用する層状珪酸塩変性脂肪族ポリアミド樹脂(A1)は、脂肪族ポリアミド樹脂を層間重合法により層状珪酸塩で変性したものである。 The layered silicate-modified aliphatic polyamide resin (A1) used in the present invention is obtained by modifying an aliphatic polyamide resin with a layered silicate by an interlayer polymerization method.
脂肪族ポリアミド樹脂は、特に限定されないが、好ましくは、ナイロン6、ナイロン610、ナイロン612、およびナイロン6.66が単独または混合物として使用でき、ナイロン610、ナイロン612、およびナイロン6.66は、好ましくは、ε−カプロラクタム由来成分を90モル%以上含むものが使用される。なかでも、ナイロン6が耐疲労性の点で好ましい。 The aliphatic polyamide resin is not particularly limited, but preferably, nylon 6, nylon 610, nylon 612, and nylon 6.66 can be used alone or as a mixture, and nylon 610, nylon 612, and nylon 6.66 are preferable. That contains 90 mol% or more of an ε-caprolactam-derived component is used. Of these, nylon 6 is preferable in terms of fatigue resistance.
脂肪族ポリアミド樹脂を変性するために用いられる層状珪酸塩は、特に限定されないが、好ましくは、モンモリロナイト、バイデライト、サポナイト、ヘクトライトなどのスメクタイト族、カオリンナイト、ハロサイトなどのカオリンナイト族、ジオクタへドラルバーミキュライト、トリオクタヘドラルバーミキュライトなどのバーミキュライト族、テニオライト、テトラシリシックマイカ、マスコバイト、イライト、セリサイト、フォロゴバイト、バイオタイトなどのマイカなどが用いられるが、なかでも、脂肪族ポリアミド樹脂との相互作用力が強いモンモリロナイトが好ましく、特にナトリウム(Na)型モンモリロナイトが好ましい。 The layered silicate used for modifying the aliphatic polyamide resin is not particularly limited, but is preferably a smectite group such as montmorillonite, beidellite, saponite and hectorite, a kaolinite group such as kaolinite and halosite, and dioctane. Vermiculite families such as Doral vermiculite and trioctahedral vermiculite, teniolite, tetrasilicic mica, mascobite, illite, sericite, phologbite, biotite, and other mica are used. Among them, aliphatic polyamide resins Montmorillonite having a strong interaction force with sodium is preferable, and sodium (Na) type montmorillonite is particularly preferable.
層状珪酸塩で脂肪族ポリアミド樹脂を変性する層間重合法とは、膨潤化剤(例えば、分子式H2N−(CH2)n−1COOHを有するω−アミノ酸のアンモニウム塩)と層状珪酸塩中金属イオンとをイオン交換し、層間を広げて、さらにモノマーを取り込ませて重合する方法をいう。変性脂肪族ポリアミド樹脂(A1)中の層状珪酸塩の含有量は、好ましくは0.5〜5質量%であり、より好ましくは1〜3質量%である。 An interlayer polymerization method in which an aliphatic polyamide resin is modified with a layered silicate is a swelling agent (for example, an ammonium salt of an ω-amino acid having the molecular formula H 2 N— (CH 2 ) n-1 COOH) and a layered silicate It refers to a method in which metal ions are ion-exchanged, the layers are expanded, and a monomer is further taken in for polymerization. The content of the layered silicate in the modified aliphatic polyamide resin (A1) is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass.
層状珪酸塩変性脂肪族ポリアミド樹脂(A1)は、市販されており、たとえば宇部興産株式会社から、ナイロン6「UBEナイロン」1022C2の名称で、2質量%のナトリウム型モンモリロナイトで変性された変性脂肪族ポリアミド樹脂が入手できる。 The layered silicate-modified aliphatic polyamide resin (A1) is commercially available, for example, from Ube Industries, Ltd. under the name of nylon 6 “UBE nylon” 1022C2, a modified aliphatic modified with 2% by mass of sodium-type montmorillonite. Polyamide resins are available.
本発明において使用する疎水性可塑剤(A2)は、フェダーズ(Fedors)の式から算出した溶解度パラメーター(SP値)が10〜12(cal/cm2)1/2であれば、特に限定されないが、例えば、芳香族エステル、脂肪族エステル、燐酸エステル、スルホンアミド系可塑剤などの公知の任意の疎水性可塑剤を用いることができ、特にスルホンアミド系可塑剤(例えば、ブチルベンゼンスルホンアミド、p−トルエンスルホンアミド、N−エチル−p−トルエンスルホンアミド、N−シクロヘキシル−p−トルエンスルホンアミド)などが、本発明で使用するポリアミド樹脂との相溶性の観点から好ましく用いられる。 The hydrophobic plasticizer (A2) used in the present invention is not particularly limited as long as the solubility parameter (SP value) calculated from the Fedors formula is 10 to 12 (cal / cm 2 ) 1/2. Any known hydrophobic plasticizer such as aromatic ester, aliphatic ester, phosphate ester, sulfonamide plasticizer can be used, and in particular, sulfonamide plasticizer (for example, butylbenzenesulfonamide, p -Toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N-cyclohexyl-p-toluenesulfonamide) and the like are preferably used from the viewpoint of compatibility with the polyamide resin used in the present invention.
ここで、溶解度パラメーター(SP値)は、フェダーズ(Fedors)の方法により決定される25℃におけるポリマーの繰り返し単位から算出される値をいう。該方法は、R.F.Fedors,Polym.Eng.Sci.,14(2),147(1974)。すなわち、求める化合物の構造式において、原子および原子団の蒸発エネルギーとモル体積のデータより次式により決定される。
溶解度パラメーター=(ΣΔei/ΣΔvi)1/2
ただし、式中、ΔeiおよびΔviは、それぞれ原子または原子団の蒸発エネルギーおよびモル体積を表す。求める化合物の構造式はIR、NMR、マススペクトルなどの通常の構造分析手法を用いて決定する。
Here, the solubility parameter (SP value) refers to a value calculated from the repeating unit of the polymer at 25 ° C. determined by the method of Fedors. The method is described in R.A. F. Fedors, Polym. Eng. Sci. , 14 (2), 147 (1974). That is, in the structural formula of the desired compound, it is determined by the following formula from the data of the evaporation energy and molar volume of atoms and atomic groups.
Solubility parameter = (ΣΔei / ΣΔvi) 1/2
However, in formula, (DELTA) ei and (DELTA) vi represent the evaporation energy and molar volume of an atom or an atomic group, respectively. The structural formula of the compound to be determined is determined using a general structural analysis technique such as IR, NMR, and mass spectrum.
熱可塑性樹脂組成物(A)中の層状珪酸塩変性脂肪族ポリアミド樹脂(A1)の含有量は60〜90質量%であり、好ましくは65〜80質量%である。熱可塑性樹脂組成物(A)中の疎水性可塑剤(A2)の含有量は10〜40質量%であり、好ましくは20〜35質量%である。疎水性可塑剤(C)の含有量が少ないと、溶融混合時に変性エチレン系改質ポリマーの酸無水物基とポリアミド樹脂との反応が進行してしまい、得られる熱可塑性エラストマー組成物の溶融粘度が著しく高くなり、加工性が悪化するので好ましくなく、逆に多いと、疎水性可塑剤が熱可塑性エラストマー組成物表面ヘブリードアウトし、ハンドリングが悪化するので好ましくない。 The content of the layered silicate-modified aliphatic polyamide resin (A1) in the thermoplastic resin composition (A) is 60 to 90% by mass, preferably 65 to 80% by mass. Content of the hydrophobic plasticizer (A2) in a thermoplastic resin composition (A) is 10-40 mass%, Preferably it is 20-35 mass%. If the content of the hydrophobic plasticizer (C) is small, the reaction between the acid anhydride group of the modified ethylene-based modified polymer and the polyamide resin proceeds during melt mixing, and the melt viscosity of the resulting thermoplastic elastomer composition However, if the amount is too large, the hydrophobic plasticizer bleeds out to the surface of the thermoplastic elastomer composition and the handling is deteriorated.
本発明において使用する酸無水物基でグラフト変性された変性エチレン系改質ポリマー(B)としては、たとえば酸無水物基でグラフト変性されたエチレン−α−オレフィン共重合体などの軟質ポリマーを用いることが好ましく、かかる酸無水物基でグラフト変性された変性エチレン系改質ポリマーは公知であり、例えば、三井化学株式会社製無水マレイン酸変性エチレン−プロピレン共重合体(タフマー(登録商標)MP−0620)、無水マレイン酸変性エチレン−ブテン共重合体(タフマー(登録商標)MP−7020)として市販されており、本発明でも加工市販品を用いることができる。 As the modified ethylene-based modified polymer (B) graft-modified with an acid anhydride group used in the present invention, for example, a soft polymer such as an ethylene-α-olefin copolymer graft-modified with an acid anhydride group is used. The modified ethylene-based modified polymer graft-modified with such an acid anhydride group is known, for example, maleic anhydride-modified ethylene-propylene copolymer (Tuffmer (registered trademark) MP-) manufactured by Mitsui Chemicals, Inc. 0620), a maleic anhydride-modified ethylene-butene copolymer (Tuffmer (registered trademark) MP-7020), and a processed commercial product can also be used in the present invention.
変性エチレン系改質ポリマー(B)は、分子中に2個以上のアミノ基を有する多官能アミンで架橋されていることが、剪断速度改善の点から、好ましい。分子中に2個以上のアミノ基を有する多官能アミンとしては、ジエチレントリアミン(DTA)、トリエチレンテトラミン(TTA)、m−キシレンジアミン(m−XDA)、メタフェニレンジアミン(MPDA)、ジアミノジフェニルメタン(DDM)などが挙げられるが、なかでもポリエチレンイミンが好ましい。分子中に2個以上のアミノ基を有する多官能アミンで架橋する方法は、特に限定されないが、熱可塑性樹脂組成物(A)および変性エチレン系改質ポリマー(B)を、それらの融解温度以上で溶融混合した後、多官能アミンで変性エチレン系改質ポリマー(B)を動的に架橋することが好ましい。ここで、動的に架橋するとは、架橋対象物を含む組成物に架橋剤を添加し、剪断応力をかけながら、架橋することをいい、具体的には架橋対象物と架橋剤を含む組成物を溶融混練することによって動的に架橋することができる。 The modified ethylene-based modified polymer (B) is preferably crosslinked with a polyfunctional amine having two or more amino groups in the molecule from the viewpoint of improving the shear rate. Examples of the polyfunctional amine having two or more amino groups in the molecule include diethylenetriamine (DTA), triethylenetetramine (TTA), m-xylenediamine (m-XDA), metaphenylenediamine (MPDA), diaminodiphenylmethane (DDM). Among them, polyethyleneimine is preferable. The method of crosslinking with a polyfunctional amine having two or more amino groups in the molecule is not particularly limited, but the thermoplastic resin composition (A) and the modified ethylene-based modified polymer (B) can be brought to their melting temperatures or higher. It is preferable to dynamically crosslink the modified ethylene-based modified polymer (B) with a polyfunctional amine after being melt-mixed in step (b). Here, dynamically cross-linking means that a cross-linking agent is added to a composition containing an object to be cross-linked, and is cross-linked while applying a shear stress. Can be dynamically cross-linked by melt kneading.
本発明の熱可塑性エラストマー組成物においては、熱可塑性樹脂組成物(A)が連続相を形成し、変性エチレン系改質ポリマー(B)が分散粒子相を形成する。熱可塑性エラストマー組成物中の変性エチレン系改質ポリマー(B)の含有量は、熱可塑性エラストマー組成物100質量部に対して70〜120質量部であり、好ましくは75〜100質量部であり、より好ましくは80〜100質量部である。熱可塑性エラストマー組成物中の変性エチレン系改質ポリマー(B)の含有量が少なすぎると、低温耐久性に劣り、逆に多すぎると、溶融時の流動性が極端に低下し、フィルム製膜性が大幅に悪化する。 In the thermoplastic elastomer composition of the present invention, the thermoplastic resin composition (A) forms a continuous phase, and the modified ethylene-based modified polymer (B) forms a dispersed particle phase. The content of the modified ethylene-based modified polymer (B) in the thermoplastic elastomer composition is 70 to 120 parts by weight, preferably 75 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer composition. More preferably, it is 80-100 mass parts. If the content of the modified ethylene-based modified polymer (B) in the thermoplastic elastomer composition is too small, the low-temperature durability is inferior. On the other hand, if the content is too large, the fluidity at the time of melting extremely decreases, and film formation Sexually deteriorates.
本発明の熱可塑性エラストマー組成物は、例えば前記層状珪酸塩変性ポリアミド樹脂(A1)と前記疎水性可塑剤(A2)とをあらかじめ、例えばポリアミド樹脂の融点より20℃高い温度で溶融混合し、次いで変性エチレン系改質ポリマー(B)を溶融混合することによって製造することができる。
In the thermoplastic elastomer composition of the present invention, for example, the layered silicate-modified polyamide resin (A1) and the hydrophobic plasticizer (A2) are previously melt-mixed at a
変性エチレン系改質ポリマー(B)を架橋するときは、層間重合法により作製した層状珪酸塩変性脂肪族ポリアミド樹脂(A1)60〜90質量%および溶解度パラメーター(SP値)が10〜12(cal/cm2)1/2である疎水性可塑剤(A2)40〜10質量%からなる熱可塑性樹脂組成物(A)100質量部と、酸無水物基でグラフト変性された変性エチレン系改質ポリマー(B)70〜120質量部とを、前記熱可塑性樹脂組成物(A)および前記変性エチレン系改質ポリマー(B)の融解温度以上で溶融混合した後、多官能アミンで前記変性エチレン系改質ポリマー(B)を動的に架橋することが好ましい。 When cross-linking the modified ethylene-based modified polymer (B), the layered silicate-modified aliphatic polyamide resin (A1) produced by the interlayer polymerization method is 60 to 90% by mass and the solubility parameter (SP value) is 10 to 12 (cal / Cm 2 ) 1/2 hydrophobic plasticizer (A2) 100 parts by mass of thermoplastic resin composition (A) composed of 40 to 10% by mass, and modified ethylene-based modification graft-modified with an acid anhydride group 70 to 120 parts by mass of the polymer (B) is melt-mixed at a temperature equal to or higher than the melting temperature of the thermoplastic resin composition (A) and the modified ethylene-based modified polymer (B), and then the modified ethylene-based polymer with a polyfunctional amine. It is preferable to dynamically crosslink the modified polymer (B).
本発明の熱可塑性エラストマー組成物には、前記した成分に加えて、カーボンブラックやシリカなどのその他の補強剤(フィラー)、加硫または架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤などの樹脂及びゴム組成物用に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量は本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 In addition to the aforementioned components, the thermoplastic elastomer composition of the present invention includes other reinforcing agents (fillers) such as carbon black and silica, vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, and anti-aging. Various additives that are generally blended for resins and rubber compositions such as additives can be blended, and such additives are kneaded by a general method to form a composition for vulcanization or crosslinking. Can be used. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used.
本発明の熱可塑性エラストマー組成物は、T型ダイス付きの押出機や、インフレーション成形機などでフィルムとすることができ、そのフィルムは、ガスバリヤ性、耐熱性、耐屈曲疲労性に優れるため、空気入りタイヤのインナーライナーとして好適に使用することができる。 The thermoplastic elastomer composition of the present invention can be formed into a film with an extruder with a T-die or an inflation molding machine, and the film is excellent in gas barrier property, heat resistance, and bending fatigue resistance. It can be suitably used as an inner liner of a entering tire.
本発明に係る熱可塑性エラストマー組成物からなるフィルムをインナーライナーとして用いた空気入りタイヤの製造方法について、インナーライナーをカーカス層の内側に配置する場合の一例を説明すると、予め本発明の熱可塑性エラストマー組成物を所定の幅と厚さのフィルム状に押し出し、それをタイヤ成形用ドラム上に円筒に貼りつける。その上に未加硫ゴムからなるカーカス層、ベルト層、トレッド層等の通常のタイヤ製造に用いられる部材を順次貼り重ね、ドラムを抜き去ってグリーンタイヤとする。次いで、このグリーンタイヤを常法に従って加熱加硫することにより、所望の空気入りタイヤを製造することができる。 An example of a method for producing a pneumatic tire using a film made of the thermoplastic elastomer composition according to the present invention as an inner liner will be described in advance, in which the inner liner is disposed inside the carcass layer. The composition is extruded in the form of a film having a predetermined width and thickness, and is stuck on a cylinder on a tire-forming drum. On top of that, members used for normal tire production such as a carcass layer, a belt layer, a tread layer and the like made of unvulcanized rubber are sequentially laminated, and the drum is removed to obtain a green tire. Next, a desired pneumatic tire can be manufactured by heating and vulcanizing the green tire according to a conventional method.
本発明の熱可塑性エラストマー組成物は、空気入りタイヤのほか、各種樹脂ホースとして、またその他各種の気体(ガス・空気等)の透過制御に係わるゴム製品、例えば、防舷材、ゴム袋、燃料タンク等に使用する積層体材料としても用いることができる。 The thermoplastic elastomer composition of the present invention is not only a pneumatic tire but also various resin hoses, and other rubber products related to permeation control of various gases (gas, air, etc.), such as fenders, rubber bags, fuels, etc. It can also be used as a laminate material used for tanks and the like.
(1)原材料
ポリアミド樹脂として、次の3種類を用いた。
ポリアミド樹脂1:層間重合法により作製した層状珪酸塩変性脂肪族ポリアミド樹脂(宇部興産株式会社製ナイロン6「UBEナイロン」1022C2、層状珪酸塩:ナトリウム型モンモリロナイト、層状珪酸塩含有量:2質量%、溶融粘度η:387Pa・s)
ポリアミド樹脂2:高粘度ナイロン6(宇部興産株式会社製ナイロン6「UBEナイロン」1022B、溶融粘度η:254Pa・s)
ポリアミド樹脂3:低粘度ナイロン6(宇部興産株式会社製ナイロン6「UBEナイロン」1013B、溶融粘度η:113Pa・s)
(1) Raw materials The following three types were used as polyamide resins.
Polyamide resin 1: Layered silicate-modified aliphatic polyamide resin prepared by interlayer polymerization (Nylon 6 “UBE nylon” 1022C2 manufactured by Ube Industries, Ltd., layered silicate: sodium montmorillonite, layered silicate content: 2% by mass, Melt viscosity η: 387 Pa · s)
Polyamide resin 2: High-viscosity nylon 6 (Nylon 6 “UBE nylon” 1022B manufactured by Ube Industries, Ltd., melt viscosity η: 254 Pa · s)
Polyamide resin 3: Low-viscosity nylon 6 (Nylon 6 “UBE nylon” 1013B manufactured by Ube Industries, Ltd., melt viscosity η: 113 Pa · s)
疎水性可塑剤として、次の4種類を用いた。
疎水性可塑剤1:n−ブチルベンゼンスルホンアミド(大八化学工業株式会社製BM−4、SP値:10.5(cal/cm2)1/2)
疎水性可塑剤2:トリクレジルホスフェート(大八化学工業株式会社製TCP、SP値:9.6(cal/cm2)1/2)
疎水性可塑剤3:ビス(ブチルジグリコール)アジペート(大八化学工業株式会社製BXA、SP値:9.5(cal/cm2)1/2)
疎水性可塑剤4:ジイソデシルフタレート(大八化学工業株式会社製DIDP、SP値:9.0(cal/cm2)1/2)
The following four types were used as hydrophobic plasticizers.
Hydrophobic plasticizer 1: n-butylbenzenesulfonamide (BM-8 manufactured by Daihachi Chemical Industry Co., Ltd., SP value: 10.5 (cal / cm 2 ) 1/2 )
Hydrophobic plasticizer 2: tricresyl phosphate (TCP manufactured by Daihachi Chemical Industry Co., Ltd., SP value: 9.6 (cal / cm 2 ) 1/2 )
Hydrophobic plasticizer 3: bis (butyldiglycol) adipate (BXA manufactured by Daihachi Chemical Industry Co., Ltd., SP value: 9.5 (cal / cm 2 ) 1/2 )
Hydrophobic plasticizer 4: Diisodecyl phthalate (DIDP manufactured by Daihachi Chemical Industry Co., Ltd., SP value: 9.0 (cal / cm 2 ) 1/2 )
酸無水物基でグラフト変性された変性エチレン系改質ポリマーとして、無水マレイン酸変性エチレン−プロピレン共重合体(三井化学株式会社製タフマー(登録商標)MP−0620)を用いた。 A maleic anhydride-modified ethylene-propylene copolymer (Tafmer (registered trademark) MP-0620 manufactured by Mitsui Chemicals, Inc.) was used as a modified ethylene-based modified polymer graft-modified with an acid anhydride group.
架橋剤として、ポリエチレンイミン(株式会社日本触媒製エポミンTMSP−006)を用いた。 Polyethyleneimine (Nippon Shokubai Epomin ™ SP-006) was used as a cross-linking agent.
(2)熱可塑性エラストマー組成物の製造
ポリアミド樹脂と疎水性可塑剤を、表1に示す質量%で、2軸混練機(日本製鋼所製TEX44)に投入し、混線機温度230℃で溶融混練し、熱可塑性樹脂組成物を得た。次いで、熱可塑性樹脂組成物100重量部と、表1に示す質量部の変性エチレン系改質ポリマーを、該当する場合はさらに架橋剤を、2軸混練機に投入し、混線機温度220℃で溶融混練し、押出機から連続してストランド状に排出し、水冷後カッターで切断することによりペレット状の熱可塑性エラストマー組成物を得た。
(2) manufacturing a polyamide resin and a hydrophobic plasticizer in the thermoplastic elastomer composition, in mass% shown in Table 1 were charged into a twin screw kneader (manufactured by Nippon Steel plants made TEX44), melting at crosstalk press temperature 230 ° C. The mixture was kneaded to obtain a thermoplastic resin composition. Next, 100 parts by weight of the thermoplastic resin composition and the modified ethylene-based modified polymer in parts by mass shown in Table 1 were added to the biaxial kneader when applicable, and the cross-linker temperature was 220 ° C. The mixture was melt-kneaded, continuously discharged from the extruder into a strand, cooled with water, and cut with a cutter to obtain a pellet-shaped thermoplastic elastomer composition.
(3)熱可塑性エラストマー組成物フィルムの製造
550mm幅T型ダイス付40mmφ単軸押出機(株式会社プラ技研製)を用いて、押出温度C1/C2/C3/C4/ダイ=200/210/230/235/235℃、冷却ロール温度50℃、引き取り速度4m/分の押出条件で、ペレット状の熱可塑性エラストマー組成物を、平均厚み150μmのフィルムに成形した。
(3) using the thermoplastic elastomer composition film production 550mm width T-die with 40mmφ single screw extruder (manufactured flops la Giken), extrusion temperature C1 / C2 / C3 / C4 / die = 200/210 / The pellet-shaped thermoplastic elastomer composition was formed into a film having an average thickness of 150 μm under the extrusion conditions of 230/235/235 ° C., a cooling roll temperature of 50 ° C., and a take-off speed of 4 m / min.
(4)試験タイヤの製造
天然ゴム(PT. NIJSIRA SIR20)20質量部、乳化重合SBR(日本ゼオン株式会社製NIPOL 1502)40質量部、ハロゲン化ブチルゴム(エクソンモービルケミカルズ社製Exxon BromButyl 2255)40質量部、カーボンブラック(東海カーボン株式会社製シースト9M)60質量部、アロマオイル(昭和シェル石油株式会社製デゾレックス3号)15質量部、および臭素化フェノール樹脂(田岡化学工業株式会社製タッキロール250−1)5質量部を、16リットルの密閉式ミキサーで5分間混練し、140℃に達したときに取り出し、マスターバッチを得た。このマスターバッチに酸化亜鉛(正同化学工業株式会社製酸化亜鉛3種)2質量部およびステアリン酸(日本油脂株式会社製ビーズステアリン酸YR)1質量部をオープンロールで混練し、ゴム組成物を得た。ゴム組成物を幅500mm、厚さ300μmに圧延成形し、未加硫ゴム組成物シートを得た。
上記の熱可塑性エラストマー組成物フィルムの片面に、上記のゴム組成物シートを積層し、これをタイヤ用インナーライナーとした。次いで、該積層体の熱可塑性エラストマー組成物フィルムが最内面になるように配置された195/65R15の乗用車用空気入りタイヤを、加硫温度178℃、加硫時間12分の条件下、常法に従って作製した。
(4) Manufacture of
The rubber composition sheet was laminated on one side of the thermoplastic elastomer composition film, and this was used as a tire inner liner. Next, a 195 / 65R15 pneumatic tire for passenger cars arranged so that the thermoplastic elastomer composition film of the laminate is the innermost surface is subjected to a conventional method under conditions of a vulcanization temperature of 178 ° C. and a vulcanization time of 12 minutes. It produced according to.
各種の物性および性能は次の方法により評価した。 Various physical properties and performance were evaluated by the following methods.
[溶融粘度]
溶融粘度とは、混練加工時の任意の温度、成分の溶融粘度をいい、各ポリマー材料の溶融粘度は、温度、剪断速度(sec-1)及び剪断応力の依存性があるため、一般に細管中を流れる溶融状態にある任意の温度、特に混練時の温度領域でのポリマー材料の応力と剪断速度を測定し、下記式より溶融粘度を測定する。
η=剪断応力/剪断速度
本発明においては、東洋精機社製キャピラリーレオメーターキャピログラフ1Cを用いて、250℃、剪断速度250sec−1において、熱可塑性エラストマー組成物の溶融粘度(Pa・s)を測定した。溶融粘度が1800Pa・s以下であることが、フィルム製膜性の観点から好ましい。
[Melt viscosity]
Melt viscosity means any temperature and melt viscosity of components at the time of kneading process. Since the melt viscosity of each polymer material is dependent on temperature, shear rate (sec -1 ) and shear stress, it is generally in a thin tube. Measure the stress and shear rate of the polymer material at an arbitrary temperature in the molten state flowing through, particularly in the temperature range during kneading, and measure the melt viscosity from the following formula.
η = shear stress / shear rate In the present invention, the melt viscosity (Pa · s) of the thermoplastic elastomer composition at 250 ° C. and a shear rate of 250 sec −1 using a capillary rheometer capilograph 1C manufactured by Toyo Seiki Co., Ltd. Was measured. A melt viscosity of 1800 Pa · s or less is preferable from the viewpoint of film formability.
[溶融成形性]
上記の「熱可塑性エラストマー組成物フィルムの製造」において、フィルムが製膜できたときは○、フィルムが製膜できなかったときは×とした。溶融成形性はフィルム製膜性の尺度である。
[Melt formability]
In the above “Production of thermoplastic elastomer composition film”, “◯” was given when the film could be produced, and “x” when the film could not be produced. Melt formability is a measure of film formability.
[変性エチレン系改質ポリマー相の平均分散粒子径]
熱可塑性エラストマー組成物を−100℃で凍結し、該試料をミクロトームにより切削し、フレッシュな面を出した後、その面を原子間力顕微鏡(エスアイアイ・ナノテクノロジー社製SPA−300HV)で観察することにより、変性エチレン系改質ポリマー相の数平均分散粒子径(μm)を測定した。
[Average dispersion particle diameter of modified ethylene-based modified polymer phase]
The thermoplastic elastomer composition was frozen at −100 ° C., the sample was cut with a microtome, and a fresh surface was formed. Then, the surface was observed with an atomic force microscope (SP-300HV manufactured by SII Nanotechnology). As a result, the number average dispersed particle size (μm) of the modified ethylene-based modified polymer phase was measured.
[定歪疲労試験(平均破断回数)]
熱可塑性エラストマー組成物を幅200mmで厚さ150μmのフィルム状に成形し、厚さ0.2cmの未加硫ゴムに貼り付けて180℃×10分間加硫した。これをJIS 2号ダンベル形状に打ち抜き、チャック間50mm、ストローク20mm、周波数6.67Hzで繰り返し変形を与え、試料が破断するまでの回数を測定し、n=5の平均値を平均破断回数とする。
[Constant strain fatigue test (average number of breaks)]
The thermoplastic elastomer composition was formed into a film having a width of 200 mm and a thickness of 150 μm, and was attached to an unvulcanized rubber having a thickness of 0.2 cm and vulcanized at 180 ° C. for 10 minutes. This was punched into a JIS No. 2 dumbbell shape, repeatedly deformed at a chuck distance of 50 mm, a stroke of 20 mm, and a frequency of 6.67 Hz, and the number of times until the sample broke was measured. The average value of n = 5 was defined as the average number of breaks. .
[タイヤ耐久試験]
165SR13スチールラジアルタイヤを作製し、13×4 1/2−Jサイズのリムに組み、空気圧を200kPaとして1500ccクラスの乗用車に装着して4名乗車時相当荷重(65kg/人)を与え、実路上を2万km走行する。走行後にタイヤをリムから外し、タイヤ内面のライナー層を目視観測する。ライナー層にクラック、目視できるような「しわ」、ライナー層の剥離・浮き上がりがあるものを不合格、ないものを合格と判定する。
[Tire durability test]
A 165SR13 steel radial tire was manufactured, assembled on a 13x4 1 / 2-J size rim, mounted on a 1500cc class passenger car with an air pressure of 200kPa, and given a load equivalent to four passengers (65kg / person). Drive 20,000km. After running, remove the tire from the rim and visually observe the liner layer on the inner surface of the tire. The liner layer is judged to be unacceptable if the liner layer has cracks, visible “wrinkles”, and the liner layer is peeled or lifted, and it is judged not to be acceptable.
[タイヤエア漏れ値]
初期圧力200kPa、室温、無負荷条件にて3か月放置する。内圧の測定間隔は4日毎とし、測定圧力Pt、初期圧力Po、経過日数tとして式
Pt/Po=exp(−αt)
に回帰してα値を求める。得られたαを用い、t=30(日)を代入して
β=〔1−exp(−αt)〕×100
により1か月あたりの空気圧低下率β(%/月)を得る。
[Tire air leak value]
Leave for 3 months at an initial pressure of 200 kPa, room temperature and no load. The measurement interval of the internal pressure is every 4 days, the measurement pressure Pt, the initial pressure Po, the elapsed days t
Pt / Po = exp (−αt)
The α value is obtained by returning to. Using the obtained α, substituting t = 30 (days)
β = [1-exp (−αt)] × 100
To obtain the air pressure decrease rate β (% / month) per month.
上記のように作製した熱可塑性エラストマー組成物、熱可塑性エラストマー組成物フィルムおよび試験タイヤについて、物性および性能を評価した結果を表1に示す。 Table 1 shows the results of evaluating the physical properties and performance of the thermoplastic elastomer composition, the thermoplastic elastomer composition film and the test tire produced as described above.
本発明の熱可塑性エラストマー組成物(実施例1〜4)は、変性エチレン系改質ポリマーの分散性を悪化させることなく、溶融粘度を低下させることができ、フィルム製膜が可能である。その熱可塑性エラストマー組成物から作製したフィルムは、定歪疲労試験において非常に大きい平均破断回数を示し、そのフィルムをインナーライナーとして用いた空気入りタイヤは、タイヤ耐久試験に合格し、タイヤエア漏れ値も小さく、優れた性能を有していた。 The thermoplastic elastomer composition (Examples 1 to 4) of the present invention can reduce the melt viscosity without deteriorating the dispersibility of the modified ethylene-based modified polymer, and can form a film. A film made from the thermoplastic elastomer composition exhibits a very large average number of breaks in the constant strain fatigue test, and a pneumatic tire using the film as an inner liner passes the tire durability test and also has a tire air leakage value. It was small and had excellent performance.
図1は、ポリアミド樹脂および疎水性可塑剤からなる熱可塑性樹脂組成物100質量部ならびに変性エチレン系改質ポリマー80質量部からなる熱可塑性エラストマー組成物において、疎水性可塑剤の種類と量が、熱可塑性エラストマー組成物の溶融粘度に及ぼす影響を図示したものである。この図から、層状珪酸塩変性脂肪族ポリアミド樹脂と溶解度パラメーター(SP値)が10〜12(cal/cm2)1/2である疎水性可塑剤の組み合わせが溶融粘度の低下に効果的であることが分かる。 FIG. 1 shows a thermoplastic elastomer composition comprising 100 parts by mass of a thermoplastic resin composition comprising a polyamide resin and a hydrophobic plasticizer and 80 parts by mass of a modified ethylene-based modified polymer. The influence which it has on the melt viscosity of a thermoplastic elastomer composition is illustrated. From this figure, a combination of a layered silicate-modified aliphatic polyamide resin and a hydrophobic plasticizer having a solubility parameter (SP value) of 10 to 12 (cal / cm 2 ) 1/2 is effective in reducing the melt viscosity. I understand that.
Claims (6)
Priority Applications (5)
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JP2008203414A JP4811436B2 (en) | 2008-08-06 | 2008-08-06 | Thermoplastic elastomer composition and pneumatic tire using the same |
KR1020090062144A KR101600087B1 (en) | 2008-08-06 | 2009-07-08 | Thermoplastic elastomer composition and pneumatic tire using the same |
US12/500,340 US20100036028A1 (en) | 2008-08-06 | 2009-07-09 | Thermoplastic elastomer composition and pneumatic tire using the same |
CN2009101598308A CN101643579B (en) | 2008-08-06 | 2009-07-10 | Thermoplastic elastomer composition and pneumatic tire using the same |
EP09165197A EP2154202B1 (en) | 2008-08-06 | 2009-07-10 | Thermoplastic Elastomer Composition and Pneumatic Tire Using the Same |
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JP2008203414A JP4811436B2 (en) | 2008-08-06 | 2008-08-06 | Thermoplastic elastomer composition and pneumatic tire using the same |
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JP4811436B2 true JP4811436B2 (en) | 2011-11-09 |
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US (1) | US20100036028A1 (en) |
EP (1) | EP2154202B1 (en) |
JP (1) | JP4811436B2 (en) |
KR (1) | KR101600087B1 (en) |
CN (1) | CN101643579B (en) |
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JP4930629B2 (en) | 2010-08-27 | 2012-05-16 | 横浜ゴム株式会社 | Thermoplastic resin composition |
US8454778B2 (en) | 2010-11-15 | 2013-06-04 | Ramendra Nath Majumdar | Pneumatic tire with barrier layer and method of making the same |
EP2692801B1 (en) * | 2011-03-31 | 2016-08-24 | Nitta Corporation | Thermoplastic resin composition having high durability |
KR101641493B1 (en) * | 2011-06-24 | 2016-07-21 | 카민 엘엘씨 | Compositions and methods for improving fluid-barrier properties of polymers and polymer products |
WO2013129627A1 (en) * | 2012-02-29 | 2013-09-06 | 株式会社ブリヂストン | Tire |
JP6021442B2 (en) * | 2012-05-28 | 2016-11-09 | 横浜ゴム株式会社 | Pneumatic tire |
JP6136240B2 (en) * | 2012-12-20 | 2017-05-31 | 横浜ゴム株式会社 | Method for producing a film for a pneumatic tire member comprising a thermoplastic resin composition |
JP6433971B2 (en) | 2013-03-13 | 2018-12-05 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Inner liner for pneumatic tire assembly |
US10308072B2 (en) * | 2015-04-29 | 2019-06-04 | Pirelli Tyre S.P.A. | Vulcanisable elastomeric materials for components of tyres comprising modified silicate fibres, and tyres thereof |
EP3440131B1 (en) * | 2016-04-06 | 2022-03-23 | Imertech Sas | Barrier composition comprising a talc particulate |
JP6949830B2 (en) * | 2016-04-26 | 2021-10-13 | Eneos株式会社 | Thermoplastic elastomer composition, its production method, and elastomer molded product |
EP3623172A4 (en) * | 2017-05-11 | 2020-12-02 | Bridgestone Corporation | Tire |
KR20220022192A (en) * | 2020-08-18 | 2022-02-25 | 현대자동차주식회사 | Polyamide Composite Resin Composition for Fuel Tube |
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JPS60181160A (en) * | 1984-02-28 | 1985-09-14 | Dainippon Ink & Chem Inc | Preparation of polyamide resin composition |
JPH0715057B2 (en) * | 1987-02-16 | 1995-02-22 | 住友化学工業株式会社 | Thermoplastic resin composition |
US6079465A (en) * | 1995-01-23 | 2000-06-27 | The Yokohama Rubber Co., Ltd. | Polymer composition for tire and pneumatic tire using same |
KR100267881B1 (en) * | 1995-11-02 | 2001-04-02 | 하기와라 세이지 | Thermoplastic elastomer composition and preparation method and low permeability hose using the same |
JP4197784B2 (en) * | 1998-11-24 | 2008-12-17 | 横浜ゴム株式会社 | Thermoplastic elastomer composition excellent in gas barrier property and laminate using the same |
US6376591B1 (en) * | 1998-12-07 | 2002-04-23 | Amcol International Corporation | High barrier amorphous polyamide-clay intercalates, exfoliates, and nanocomposite and a process for preparing same |
US6617383B2 (en) * | 2000-04-11 | 2003-09-09 | The Yokohama Rubber Co., Ltd. | Thermoplastic elastomer composition having improved processability and tire using the same |
KR100550254B1 (en) * | 2002-12-17 | 2006-02-08 | 제일모직주식회사 | Thermoplastic Nanocomposite Composition with High Impact Strength at Low Temperature |
KR100616723B1 (en) * | 2005-04-15 | 2006-08-28 | 주식회사 이폴리머 | Nanocomposite composition containing regenerated polyamide |
JP5328358B2 (en) * | 2005-10-27 | 2013-10-30 | エクソンモービル ケミカル パテンツ,インコーポレイティド | Low permeability thermoplastic elastomer composition |
CN102675662B (en) * | 2006-03-03 | 2014-08-20 | 横滨橡胶株式会社 | Elastomer composition, method for producing same, and pneumatic tire using same |
JP4163219B2 (en) * | 2006-04-27 | 2008-10-08 | 横浜ゴム株式会社 | Thermoplastic elastomer and thermoplastic elastomer composition |
JP2008069190A (en) * | 2006-09-12 | 2008-03-27 | Ube Ind Ltd | High-rigidity and low-temperature impact-resistant polyamide resin composition |
JP5473606B2 (en) * | 2007-01-18 | 2014-04-16 | 横浜ゴム株式会社 | Polyamide resin composition having excellent extensibility and bending fatigue, and pneumatic tire and hose using the same |
-
2008
- 2008-08-06 JP JP2008203414A patent/JP4811436B2/en not_active Expired - Fee Related
-
2009
- 2009-07-08 KR KR1020090062144A patent/KR101600087B1/en not_active IP Right Cessation
- 2009-07-09 US US12/500,340 patent/US20100036028A1/en not_active Abandoned
- 2009-07-10 CN CN2009101598308A patent/CN101643579B/en not_active Expired - Fee Related
- 2009-07-10 EP EP09165197A patent/EP2154202B1/en not_active Not-in-force
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KR20100018451A (en) | 2010-02-17 |
KR101600087B1 (en) | 2016-03-04 |
EP2154202A3 (en) | 2011-04-20 |
JP2010037465A (en) | 2010-02-18 |
EP2154202B1 (en) | 2012-06-27 |
US20100036028A1 (en) | 2010-02-11 |
CN101643579A (en) | 2010-02-10 |
EP2154202A2 (en) | 2010-02-17 |
CN101643579B (en) | 2013-01-02 |
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